US8207244B2 - Visible light absorbers for ophthalmic lens materials - Google Patents

Visible light absorbers for ophthalmic lens materials Download PDF

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US8207244B2
US8207244B2 US12/830,149 US83014910A US8207244B2 US 8207244 B2 US8207244 B2 US 8207244B2 US 83014910 A US83014910 A US 83014910A US 8207244 B2 US8207244 B2 US 8207244B2
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ophthalmic device
device material
methacrylate
azo compound
compound
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US20110003910A1 (en
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Walter R. Laredo
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Alcon Inc
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Novartis AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/18—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
    • C09B43/20—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group with monocarboxylic acids, carbamic acid esters or halides, mono- isocyanates or haloformic acid esters
    • C09B43/202—Aliphatic, cycloaliphatic, araliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
    • G02C7/108—Colouring materials

Definitions

  • This invention is directed to visible light absorbers.
  • this invention relates to novel azo compound monomers especially suitable for use in implantable ophthalmic lens materials.
  • Both UV and visible light absorbers are known as ingredients for polymeric materials used to make ophthalmic lenses, and such absorbers may be used in combination with each other. These absorbers are preferably covalently bound to the polymeric network of the lens material instead of simply physically entrapped in the material to prevent them from migrating, phase separating or leaching out of the lens material. Such stability is particularly important for implantable ophthalmic lenses where the leaching of the absorber may present both toxicological issues and lead to the loss of visible light blocking activity in the implant.
  • absorbers contain conventional olefinic polymerizable groups, such as methacrylate, acrylate, methacrylamide, acrylamide or styrene groups. Copolymerization with other ingredients in the lens materials, typically with a radical initiator, incorporates the absorbers into the resulting polymer chain. Incorporation of additional functional groups on an absorber may influence one or more of the absorber's light-absorbing properties, solubility or reactivity. If the absorber does not have sufficient solubility in the remainder of the ophthalmic lens material ingredients or polymeric lens material, the absorber may coalesce into domains that could interact with light and result in decreased optical clarity of the lens.
  • olefinic polymerizable groups such as methacrylate, acrylate, methacrylamide, acrylamide or styrene groups.
  • visible light absorbers suitable for use in intraocular lenses can be found in U.S. Pat. No. 5,470,932. What is needed are additional visible light absorbing compounds that are copolymerizable with other ingredients in implantable lens materials, relatively inexpensive to synthesize, and are efficient in absorbing light between approximately 380-495 nm.
  • the present invention provides novel azo compounds that satisfy the above objectives. These azo compounds are especially suitable for use as monomers that absorb a portion of visible light (approximately 380-495 nm). These absorbers are suitable for use in ophthalmic lenses, including contact lenses. They are particularly useful in implantable lenses, such as intraocular lenses (IOLs).
  • IOLs intraocular lenses
  • the azo compounds of the present invention contain reactive groups, which allow for covalent attachment of the absorbers to ocular lens materials. Additionally, the absorbers of the present invention can be synthesized in approximately 3-4 steps from readily available, inexpensive starting materials without the need for column chromatography.
  • the present invention also relates to ophthalmic device materials containing such azo compounds
  • FIGS. 1-4 show percent transmittance curves for Compounds A-C at various concentrations.
  • FIG. 5 shows the percent transmittance curve for a combination of Compound A and the UV absorber (“UV-1”).
  • FIG. 6 shows the photostability results for the formulation of Example 11D after light exposure equivalent to 20 years
  • the azo compounds of the present invention have the following structure:
  • Preferred compounds of Formula I are those wherein
  • More preferred compounds of Formula I are the following three compounds: 2-hydroxy-3-((4-methoxyphenyl)diazenyl)-5-methylbenzyl methacrylate (“Compound A”); 2-hydroxy-5-methyl-3-((3,4,5-trimethoxy-phenyl)diazenyl)benzyl methacrylate (“Compound B”); and 5-chloro-2-hydroxy-3-((4-methoxyphenyl)diazenyl)benzyl methacrylate (“Compound C”).
  • the azo compounds of the present invention are suitable for use in ophthalmic device materials, particularly IOLs.
  • IOL materials will generally contain from 0.005 to 0.2% (w/w) of a compound of Formula I.
  • IOL materials will contain from 0.01 to 0.08% (w/w) of a compound of the present invention.
  • IOL materials will contain from 0.01 to 0.05% (w/w) of a compound of the present invention.
  • Such device materials are prepared by copolymerizing the compounds of Formula I with other ingredients, such as device-forming materials, cross-linking agents.
  • the IOL or other ophthalmic device materials containing the compounds of Formula I optionally contain UV absorbers and other visible light absorbers.
  • the ophthalmic device materials comprise an acrylic or methacrylic device-forming monomer. More preferably, the device-forming monomers comprise a monomer of formula II:
  • Preferred monomers of formula II are those wherein A is H or CH 3 , B is (CH 2 ) m , m is 2-5, Y is nothing or O, w is 0-1, and D is H. Most preferred are 2-phenylethyl methacrylate; 4-phenylbutyl methacrylate; 5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and 3-benzyloxypropyl methacrylate; and their corresponding acrylates.
  • Monomers of formula II are known and can be made by known methods.
  • the conjugate alcohol of the desired monomer can be combined in a reaction vessel with methyl methacrylate, tetrabutyl titanate (catalyst), and a polymerization inhibitor such as 4-benzyloxy phenol.
  • the vessel can then be heated to facilitate the reaction and distill off the reaction by-products to drive the reaction to completion.
  • Alternative synthesis schemes involve adding methacrylic acid to the conjugate alcohol and catalyzing with a carbodiimide or mixing the conjugate alcohol with methacryloyl chloride and a base such as pyridine or triethylamine.
  • Device materials generally comprise a total of at least about 75%, preferably at least about 80%, of device-forming monomers.
  • the device materials of the present invention generally comprise a cross-linking agent.
  • the cross-linking agent used in the device materials of this invention may be any terminally ethylenically unsaturated compound having more than one unsaturated group.
  • a preferred cross-linking monomer is CH 2 ⁇ C(CH 3 )C( ⁇ O)O—(CH 2 CH 2 O) p —C( ⁇ O)C(CH 3 ) ⁇ CH 2 where p is such that the number-average molecular weight is about 400, about 600, or about 1000.
  • the total amount of the cross-linking component is at least 0.1% by weight and, depending on the identity and concentration of the remaining components and the desired physical properties, can range to about 20% by weight.
  • the preferred concentration range for the cross-linking component is 1-5% for small, hydrophobic compounds with molecular weights typically less than 500 Daltons, and 5-17% (w/w) for larger, hydrophilic compounds with molecular weights typically between 500-5000 Daltons.
  • Suitable polymerization initiators for device materials containing a compound of the present invention include thermal initiators and photoinitiators.
  • Preferred thermal initiators include peroxy free-radical initiators, such as t-butyl (peroxy-2-ethyl)hexanoate and di-(tert-butylcyclohexyl)peroxydicarbonate (commercially available as Perkadox® 16 from Akzo Chemicals Inc., Chicago, Ill.). Initiators are typically present in an amount of about 5% (w/w) or less. Because free-radical initiators do not become chemically a part of the polymers formed, the total amount of initiator is customarily not included when determining the amounts of other ingredients.
  • the device materials containing an azo compound of the present invention optionally also contain a UV absorber and/or other visible light absorber.
  • a UV absorber and/or other visible light absorber are known.
  • Preferred UV absorbers include those disclosed in commonly assigned, co-pending U.S. Provisional Patent Application Ser. No. 61/111,204, filed Nov. 4, 2008. UV absorbers are typically present in intraocular lens materials.
  • the materials of the present invention may also contain other ingredients, including but not limited to agents to reduce tack or glistenings.
  • agents to reduce tack are those disclosed in U.S. Publication Nos. 2009/0132039 A1 and 2009/0137745 A1.
  • agents to reduce glistenings are those disclosed in U.S. Publication Nos. 2009/0093604 A1 and 2009/0088544 A1.
  • the IOLs constructed of the materials of the present invention can be of any design capable of being rolled or folded into, a small cross section that can fit through a relatively smaller incision.
  • the IOLs can be of what is known as a one piece or multipiece design, and comprise optic and haptic components.
  • the optic is that portion which serves as the lens.
  • the haptics are attached to the optic and hold the optic in its proper place in the eye.
  • the optic and haptic(s) can be of the same or different material.
  • a multipiece lens is so called because the optic and the haptic(s) are made separately and then the haptics are attached to the optic.
  • the optic and the haptics are formed out of one piece of material. Depending on the material, the haptics are then cut, or lathed, out of the material to produce the IOL.
  • the materials of the present invention are also suitable for use in other ophthalmic devices, such as contact lenses, keratoprostheses, and corneal inlays or rings.
  • This compound can be functionalized with pendant (meth)acrylate groups (according to Formula I) by various esterification routes.
  • the compound is dissolved in anhydrous tetrahydrofuran or dichloromethane containing MEHQ as inhibitor and pyridine as HCl acceptor.
  • MEHQ as inhibitor
  • pyridine as HCl acceptor.
  • methacryloyl chloride is added dropwise at ⁇ 20-0° C.
  • the cooling bath is removed and the reaction mixture is allowed to stir at ambient temperature for 20 hours.
  • HCl salts are removed by filtration and the organic layer is washed with 0.5-1N HCl, dried with MgSO 4 or Na 2 SO 4 , and then concentrated under reduced pressure to give the crude product, which is recrystallized in methanol or ethanol to give the desired product.
  • Other standard esterification routes known to those skilled in the art include methacrylic anhydride and methyl methacrylate routes.
  • the reaction mixture was stirred for 1 hour at ⁇ 20° C. and then 20 hours at ambient temperature.
  • the solid was filtered and diethyl ether (200 ml) and ethyl acetate (200 ml) were added to the filtrate.
  • the organic layer was washed with 0.5 N HCl, and then dried over magnesium sulfate.
  • the solvent was removed under removed pressure and the crude product was recrystallized in methanol to give an orange solid which was rinsed with cold ethanol and then for 20 hours under vacuum (0.1 mm Hg) at room temperature to afford 7.0 g (64%).
  • the solid was suspended in ⁇ 800 ml water, and acidified with 70 ml glacial acetic acid. The mixture was cooled to 0° C., filtered, and the solid was suspended in 500 ml water, cooled to 0° C., and filtered. The off-white solid was dried under vacuum to give 43.8 g (30%).
  • This compound may be esterified according to known methods (see Example 1 above).
  • reaction mixture was stirred for 20 hours at ambient temperature and then poured into 3.5 L deionized water and acidified to pH 4-5 with 1 N HCl.
  • the solid was filtered, rinsed with ample amounts of water, and dried under vacuum (0.1 mm Hg) to afford 16.64 g (52%) of a dark solid.
  • this compound may be esterified according to known methods (see Example 1 above).
  • reaction mixture was stirred for an additional 1 hour.
  • 300 mg sulfamic acid (Aldrich) was added to destroy excess nitrite and the mixture was stirred for an additional 20 minutes.
  • (2-hydroxy-5-methyl-1,3-phenylene)dimethanol (95%, Aldrich) was dissolved in 400 ml 50/50 deionized water/ethanol.
  • the diazonium mixture and remaining NaOH solution were added simultaneously to the (2-hydroxy-5-methyl-1,3-phenylene)dimethanol mixture over 60 minutes.
  • the reaction mixture was stirred for 20 hours at room temperature and then poured into 3.5 L deionized water and acidified to pH 4-5 with 1 N HCl.
  • the solid was filtered and dried under high vacuum until constant weight to afford 17.8 g (70%) of an orange solid.
  • this compound may be esterified according to known methods (see Example 1 above).
  • Transmittance curves for Compounds A-C were generated by UV/Vis spectroscopy. Each compound was dissolved in chloroform at the indicated concentration and evaluated in a PerkinElmer Lambda 35 UV/Vis spectrometer. The results are shown in FIGS. 1-4 . Additionally, a transmittance curve for a combination of Compound A and the UV absorber 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (“UV-1”; shown below) was generated using the same is procedure. The results for this combination are shown in FIG. 5 .
  • Compounds of Formula I may be formulated in IOL materials as shown in Tables 1-3 below. All components are vortex mixed in a 30 ml glass vial, degassed with nitrogen, and then syringe filtered using a 0.2 micron Teflon filter into polypropylene molds. Samples are thermally cured at 70° C. for 1 hour and 110° C. for 2 hours and then extracted in acetone at 50° C. for 6 hours with fresh solvent replacement every 90 minutes.
  • Samples of Formulation 11D were subject to UV radiation from 300 to 800 nm using an Atlas Suntest CPS+ test chamber (Atlas Electric Devices Company, Chicago, Ill.) utilizing a xenon arc lamp with light intensity of approximately 8-10 mW/cm 2 at the height of the test sample.
  • the temperature of the PBS medium was 35° C.
US12/830,149 2009-07-06 2010-07-02 Visible light absorbers for ophthalmic lens materials Active 2030-08-06 US8207244B2 (en)

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EP (1) EP2451875B1 (fr)
JP (1) JP5732456B2 (fr)
KR (1) KR101715689B1 (fr)
CN (1) CN102471597A (fr)
AR (1) AR077449A1 (fr)
AU (1) AU2010270759B2 (fr)
BR (1) BR112012000419B1 (fr)
CA (1) CA2765216C (fr)
ES (1) ES2433077T3 (fr)
HK (1) HK1164353A1 (fr)
IL (1) IL216874A (fr)
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PL (1) PL2451875T3 (fr)
RU (1) RU2534127C2 (fr)
SG (1) SG177556A1 (fr)
TW (1) TWI487690B (fr)
WO (1) WO2011005713A2 (fr)
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US8475691B2 (en) * 2011-08-15 2013-07-02 Novartis Ag UV-absorbers for ophthalmic lens materials
US8585938B1 (en) 2012-03-30 2013-11-19 Novartis Ag UV-absorbers for ophthalmic lens materials
WO2016100188A1 (fr) 2014-12-16 2016-06-23 Novartis Ag Copolymères hydrophobes d'acrylamide-acrylate pour dispositifs ophtalmiques
WO2016100190A1 (fr) 2014-12-16 2016-06-23 Novartis Ag Copolymères d'acrylate acrylamide à faible teneur en eau pour dispositifs ophtalmiques
WO2018224935A1 (fr) 2017-06-05 2018-12-13 Novartis Ag Matériaux de lentille intraoculaire d'indice de réfraction élevé et nombre d'abbe élevé
WO2018229653A1 (fr) 2017-06-13 2018-12-20 Novartis Ag Compositions de lentilles intraoculaires
US10254567B2 (en) 2016-02-22 2019-04-09 Novartis Ag UV-absorbing vinylic monomers and uses thereof
US10268053B2 (en) 2016-02-22 2019-04-23 Novartis Ag UV/visible-absorbing vinylic monomers and uses thereof
US10322993B2 (en) 2015-12-02 2019-06-18 Novartis Ag Water-soluble UV-absorbing compounds and uses thereof
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
WO2021067579A1 (fr) 2019-10-04 2021-04-08 Alcon Inc. Lentilles intraoculaires réglables et procédés de réglage postopératoire de lentilles intraoculaires
US11543683B2 (en) 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US11958824B2 (en) 2019-06-28 2024-04-16 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment

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CA2794726C (fr) 2010-04-29 2018-08-14 Novartis Ag Lentilles intraoculaires contenant des combinaisons d'absorbeurs d'uv et de chromophores de lumiere bleue
CN102617784B (zh) * 2011-02-01 2016-08-17 爱博诺德（北京）医疗科技有限公司 具有高折射率的丙烯酸类聚合物材料
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TWI513768B (zh) 2011-06-01 2015-12-21 Novartis Ag 疏水性丙烯酸系眼內水晶體材料
TWI551646B (zh) 2011-06-03 2016-10-01 諾華公司 疏水性丙烯酸系眼內水晶體材料
CN104387799B (zh) * 2013-06-27 2016-09-07 上海安诺其集团股份有限公司 一种可聚合偶氮染料化合物
WO2018036543A1 (fr) * 2016-08-25 2018-03-01 广东东阳光药业有限公司 Composé azoïque, polymère, procédé de préparation et utilisation
JP6784720B2 (ja) 2018-06-01 2020-11-11 上海富吉医療器械有限公司Ｓｈａｎｇｈａｉ Ｃｈａｒｔｗｅｌｌ Ｍｅｄｉｃａｌ Ｉｎｓｔｒｕｍｅｎｔ Ｃｏ．， Ｌｔｄ． ポリマー材料および眼内レンズ

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US9864102B2 (en) 2014-12-16 2018-01-09 Novartis Ag Hydrophobic acrylate-acrylamide copolymers for ophthalmic devices
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WO2011005713A2 (fr) 2011-01-13
MX2012000330A (es) 2012-02-08
ES2433077T3 (es) 2013-12-09
TWI487690B (zh) 2015-06-11
RU2012103837A (ru) 2013-08-20
PL2451875T3 (pl) 2014-03-31
EP2451875B1 (fr) 2013-08-28
RU2534127C2 (ru) 2014-11-27
SG177556A1 (en) 2012-02-28
AU2010270759A1 (en) 2012-01-19
KR20120089438A (ko) 2012-08-10
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ZA201109177B (en) 2013-02-27
WO2011005713A3 (fr) 2011-03-31
BR112012000419B1 (pt) 2019-10-22
HK1164353A1 (en) 2012-09-21
AR077449A1 (es) 2011-08-31
BR112012000419A2 (pt) 2016-04-05
JP2012532244A (ja) 2012-12-13
CA2765216A1 (fr) 2011-01-13
US20110003910A1 (en) 2011-01-06
CN102471597A (zh) 2012-05-23
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EP2451875A2 (fr) 2012-05-16
KR101715689B1 (ko) 2017-03-13

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